Strong Nucleophiles Research Articles

DFT study on the effects of substituents on the structure and properties of dithiophosphate collectors

AbstractThe structures and properties of seven substituted dithiophosphate (DTP) collectors containing three types of functional groups (O2PS2, C2PS2, and N2PS2) were studied using density functional theory. The collectors studied were dibutyl dithiophosphate (DNBDTP), diisobutyl dithiophosphate (DIBDTP), dibutoxyethyl dithiophosphate (DBOEDTP), xylenol dithiophosphate (DMPDTP), diisobutyl dithiohypophosphite (3418A), diphenylamine dithiophosphate (DTADTP), and dicyclohexylamine dithiophosphate (DCADTP). The structural analysis showed that the PS bond lengths in the C2PS2 and N2PS2 types are longer than those in the O2PS2 type, indicating that the strength of the PS bond is weaker in the former two. The frontier molecular orbital studies showed that the energy differences between the highest occupied molecular orbitals (HOMO) of 3418A (C2PS2 type) and DCADTP (N2PS2 type) and the lowest unoccupied molecular orbital (LUMO) of galena are significantly lower than those of the other collectors, suggesting that C2PS2 type and N2PS2 type with cyclohexane could enhance the interaction with galena. Using the Fukui function to calculate the nucleophilicity and electrophilicity of the sulfur atom indicated that the S atom exhibits nucleophilicity, especially in DMPDTP and DTADTP, which contain benzene rings, and the S atom exhibits strong nucleophilicity without electrophilicity. However, due to the lack of contribution from S atoms to the LUMO orbitals, the S atoms in these two compounds are not participate in any LUMO reactions. The adsorption results demonstrated that 3418A (C2PS2 type) and DCADTP (N2PS2 type) exhibit the strongest adsorption on Pb2+ ions, while DMPDTP (C2PS2 type) and DTADTP (O2PS2 type) which contain benzene rings, as well as DBOEDTP (C2PS2 type) which does not contain a benzene ring, exhibit weaker interaction compared to the other compounds. These are consistent with the results of the frontier molecular orbital and electrophilic nucleophilicity calculations.

Oligodeoxynucleotide Synthesis Under Non-Nucleophilic Deprotection Conditions.

This protocol describes a method for the incorporation of sensitive functional groups into oligodeoxynucleotides (ODNs). The nucleophile-sensitive epigenetic N4-acetyldeoxycytosine (4acC) DNA modification is used as an example, but other sensitive groups can also be incorporated, e.g., alkyl halide, α-haloamide, alkyl ester, aryl ester, thioester, and chloropurine groups, all of which are unstable under the basic and nucleophilic deprotection and cleavage conditions used in standard ODN synthesis methods. The method uses a 1,3-dithian-2-yl-methoxycarbonyl (Dmoc) group that carries a methyl group at the carbon of the methoxy moiety (meDmoc) for the protection of exo-amines of nucleobases. The growing ODN is anchored to a solid support via a Dmoc linker. With these protecting and linking strategies, ODN deprotection and cleavage are achieved without using any strong bases and nucleophiles. Instead, they can be carried out under nearly neutral non-nucleophilic oxidative conditions. To increase the length of ODNs that can be synthesized using the meDmoc method, the protocol also describes the synthesis of a PEGylated Dmoc (pDmoc) phosphoramidite. With some of the nucleotides being incorporated with pDmoc-CE phosphoramidite, the growing ODN on the solid support carries PEG moieties and becomes more soluble, thus enabling longer ODN synthesis. The ODN synthesis method described in this protocol is expected to make many sensitive ODNs that are difficult to synthesize accessible to researchers in multiple areas, such as epigenetics, nanopore sequencing, nucleic acid-protein interactions, antisense drug development, DNA alkylation carcinogenesis, and DNA nanotechnology. © 2024 Wiley Periodicals LLC. Basic Protocol: Sensitive ODN synthesis Support Protocol 1: Synthesis of meDmoc-CE phosphoramidites Support Protocol 2: Synthesis of a pDmoc-CE phosphoramidite.

Recent research progress on building C-N bonds via electrochemical NOx reduction.

The release of NOx species (such as nitrate, nitrite and nitric oxide) into water and the atmosphere due to human being's agricultural and industrial activities has caused a series of environmental problems, including accumulation of toxic pollutants that are dangerous to humans and animals, acid rain, the greenhouse effect and disturbance of the global nitrogen cycle balance. Electrosynthesis of organonitrogen compounds with NOx species as the nitrogen source offers a sustainable strategy to upgrade the waste NOx into value-added organic products under ambient conditions. The electrochemical reduction of NOx species can generate surface-adsorbed intermediates such as hydroxylamine, which are usually strong nucleophiles and can undergo nucleophilic attack to carbonyl groups to build C-N bonds and generate organonitrogen compounds such as amine, oxime, amide and amino acid. This mini-review summarizes the most recent progress in building C-N bonds via the in situ generation of nucleophilic intermediates from electrochemical NOx reduction, and highlights some important strategies in facilitating the reaction rates and selectivities towards the C-N coupling products. In particular, the preparation of high-performance electrocatalysts (e.g., nano-/atomic-scale catalysts, single-atom catalysts, alloy catalysts), selection of nucleophilic intermediates, novel design of reactors and understanding the surface adsorption process are highlighted. A few key challenges and knowledge gaps are discussed, and some promising research directions are also proposed for future advances in electrochemical C-N coupling.

Mechanism of photocatalytic CO2 reduction to HCO2H by a robust multifunctional iridium complex.

The tetradentate PNNP-type IrIII complex Mes-IrPCY2 ([Cl-IrIII-H]+) is reported to be an efficient catalyst for the reduction of CO2 to formate with excellent selectivity under visible light irradiation. Density functional calculations have been carried out to elucidate the mechanism and the origin of selectivity in the present work. Calculations suggest that the double-reduced complex 1-H (1[IrI-H]0) demonstrates higher activity than the single-reduced complex 2-H (2[IrIII(L˙-)-H]+), possibly owing to the higher hydride donor ability of the former compared to the latter; thus 1-H functions as the active species in the overall CO2 reduction reaction. In the HCOO- formation pathway, the hydride of 1-H performs a nucleophilic attack on CO2via an outer-sphere fashion to generate species 1-OCHO (1[IrI-OCHO]0), which then releases HCOO- to produce an IrI intermediate. A subsequent protonation and chloride coordination of the Ir center leads to the regeneration of catalyst 1[Cl-IrIII-H]+. For the CO production, a nucleophilic attack on CO2 takes place by the Ir atom of 1-Hvia an inner-sphere manner to afford complex O2C-3-H (1[O2C-IrIII-H]0), followed by a two-proton-one-electron reduction to furnish the OC-2-H complex (2[OC-IrIII(L˙-)-H]+) after liberating a H2O. Ultimately, CO is released to form 2-H. The stronger nucleophilicity as well as smaller steric hindrance of the hydride than the Ir atom of the active species 1-H (1[IrI-H]0) is found to account for the favoring of formate formation over CO formation. Meanwhile, the CO2 reduction reaction is calculated to be preferred over the hydrogen evolution reaction, and this is consistent with the experimental product distributions.

Organocatalytic aromatization-promoted umpolung reaction of imines.

The umpolung functionalization of imines bears vast synthetic potential, but polarity inversion is less efficient compared with the carbonyl counterparts. Strong nucleophiles are often required to react with the N-electrophiles without catalytic and stereochemical control. Here we show an effective strategy to realize umpolung of imines promoted by organocatalytic aromatization. The attachment of strongly electron-withdrawing groups to imines could enhance the umpolung reactivity by both electronegativity and aromatic character, enabling the direct amination of (hetero)arenes with good efficiencies and stereoselectivities. Additionally, the application of chiral Brønsted acid catalyst furnishes (hetero)aryl C-N atropisomers or enantioenriched aliphatic amines via dearomative amination from N-electrophilic aromatic precursors. Control experiments and density functional theory calculations suggest an ionic mechanism for the umpolung reaction of imines. This disconnection expands the options to forge C-N bonds stereoselectively on (hetero)arenes, which represents an important synthetic pursuit, especially in medicinal chemistry.

Synthetic Strategies of N-Heterocyclic Olefin (NHOs) and Their Recent Application of Organocatalytic Reactions and Beyond.

N-heterocyclic olefins (NHOs) derivatives have an electron-rich as well as highly polarized carabon-carbon (C=C) double bond because of the electron-donating nature of nitrogen and sulphur atoms. While NHOs have been developing as novel organocatalysts and ligands for transition metal complexes in various organic compound syntheses, different research groups are currently interested in preparing imidazole and triazolium-based chiral NHO catalysts. Some of them have been used for enantioselective organic transformations, but were still elusive. N-Heterocyclic Olefins, the alkylidene derivatives of N-heterocyclic carbenes (NHC) have shown promising results as effective promoters for numerous organic syntheses such as asymmetric catalysis, hydroborylation, hydrosilylation, reduction, CO2 sequestration, alkylation, cycloaddition, polymerization and the ring-opening reaction of aziridine and epoxides, esterification, C-F bond functionalization, amine coupling, trifluoromethyl thiolation, amination etc. NHOs catalysts with suitable structure can serve as a novel class of Lewis/Bronsted bases with strong basicity and high nucleophilicity properties. These facts strongly suggest their enormous chemical potential as sustainable catalysts for a wide variety of reactions in synthetic chemistry. The synthesis of NHOs and their properties are briefly reviewed in this article, along with a summary of the imidazole and triazole core of NHOs' most recent catalytic uses.

Bromine-Enhanced Generation and Epoxidation of Ethylene in Tandem CO2 Electrolysis Towards Ethylene Oxide.

The indirect electro-epoxidation of ethylene (C2 H4 ), produced from CO2 electroreduction (CO2 R), holds immense promise for CO2 upcycling to valuable ethylene oxide (EO). However, this process currently has a mediocre Faradaic efficiency (FE) due to sluggish formation and rapid dissociation of active species, as well as reductive deactivation of Cu-based electrocatalysts during the conversion of C2 H4 to EO and CO2 to C2 H4 , respectively. Herein, we report a bromine-induced dual-enhancement strategy designed to concurrently promote both C2 H4 -to-EO and CO2 -to-C2 H4 conversions, thereby improving EO generation, using single-atom Pt on N-doped CNTs (Pt1 /NCNT) and Br- -bearing porous Cu2 O as anode and cathode electrocatalysts, respectively. Physicochemical characterizations including synchrotron X-ray absorption, operando infrared spectroscopy, and quasi in situ Raman spectroscopy/electron paramagnetic resonance with theoretical calculations reveal that the favorable Br2 /HBrO generation over Pt1 /NCNT with optimal intermediate binding facilitates C2 H4 -to-EO conversion with a high FE of 92.2 %, and concomitantly, the Br- with strong nucleophilicity protects active Cu+ species in Cu2 O effectively for improved CO2 -to-C2 H4 conversion with a FE of 66.9 % at 800 mA cm-2 , superior to those in the traditional chloride-mediated case. Consequently, a single-pass FE as high as 41.1 % for CO2 -to-EO conversion can be achieved in a tandem system.

Bromine‐Enhanced Generation and Epoxidation of Ethylene in Tandem CO2 Electrolysis Towards Ethylene Oxide

AbstractThe indirect electro‐epoxidation of ethylene (C2H4), produced from CO2 electroreduction (CO2R), holds immense promise for CO2 upcycling to valuable ethylene oxide (EO). However, this process currently has a mediocre Faradaic efficiency (FE) due to sluggish formation and rapid dissociation of active species, as well as reductive deactivation of Cu‐based electrocatalysts during the conversion of C2H4 to EO and CO2 to C2H4, respectively. Herein, we report a bromine‐induced dual‐enhancement strategy designed to concurrently promote both C2H4‐to‐EO and CO2‐to‐C2H4 conversions, thereby improving EO generation, using single‐atom Pt on N‐doped CNTs (Pt1/NCNT) and Br−‐bearing porous Cu2O as anode and cathode electrocatalysts, respectively. Physicochemical characterizations including synchrotron X‐ray absorption, operando infrared spectroscopy, and quasi in situ Raman spectroscopy/electron paramagnetic resonance with theoretical calculations reveal that the favorable Br2/HBrO generation over Pt1/NCNT with optimal intermediate binding facilitates C2H4‐to‐EO conversion with a high FE of 92.2 %, and concomitantly, the Br− with strong nucleophilicity protects active Cu+ species in Cu2O effectively for improved CO2‐to‐C2H4 conversion with a FE of 66.9 % at 800 mA cm−2, superior to those in the traditional chloride‐mediated case. Consequently, a single‐pass FE as high as 41.1 % for CO2‐to‐EO conversion can be achieved in a tandem system.

Tellurium with Reversible Six-Electron Transfer Chemistry for High-Performance Zinc Batteries.

Chalcogens, especially tellurium (Te), as conversion-type cathodes possess promising prospects for zinc batteries (ZBs) with potential rich valence supply and high energy density. However, the conversion reaction of Te is normally restricted to the Te2-/Te0 redox with a low voltage plateau at ∼0.59 V (vs Zn2+/Zn) rather than the expected positive valence conversion of Te0 to Ten+, inhibiting the development of Te-based batteries toward high output voltage and energy density. Herein, the desired reversible Te2-/Te0/Te2+/Te4+ redox behavior with up to six-electron transfer was successfully activated by employing a highly concentrated Cl--containing electrolyte (Cl- as strong nucleophile) for the first time. Three flat discharge plateaus located at 1.24, 0.77, and 0.51 V, respectively, are attained with a total capacity of 802.7 mAh g-1. Furthermore, to improve the stability of Ten+ products and enhance the cycling stability, a modified ionic liquid (IL)-based electrolyte was fabricated, leading to a high-performance Zn∥Te battery with high areal capacity (7.13 mAh cm-2), high energy density (542 Wh kgTe-1 or 227 Wh Lcathdoe+anode-1), excellent cycling performance, and a low self-discharge rate based on 400 mAh-level pouch cell. The results enhance the understanding of tellurium chemistry in batteries, substantially promising a remarkable route for advanced ZBs.

Reactions of 2,4‐dinitrophenyl 5‐substituted‐2‐thiophenecarboxylate promoted by 4‐ZC6H4O−/4‐ZC6H4OH in 20 mol% DMSO(aq). Effects of leaving group and nucleophile on the acyl transfer reactions

AbstractThe kinetics of nucleophilic substitution reactions involving 2,4‐dinitrophenyl 5‐substituted‐2‐thiophenecarboxylate were studied kinetically with 4‐Z‐C6H4O−/4‐Z‐C6H4OH, which facilitated the reactions, in 20 mol% DMSO(aq). The reactions followed second‐order kinetics and exhibited βacyl = −2.34 to −2.92, ρ(Y) = 2.71–3.39, βnuc = 0.74–0.83, and |βlg| = 0.40–0.57. Based on the interpretation of the results, we have concluded that the reaction follows an addition–elimination mechanism in which the first step is the rate‐determining step (rds). The transition state structures for the 4‐ZC6H4O−‐promoted reactions remained nearly the same with a change in the leaving group from 4‐nitrophenoxide to 2,4‐dinitrophenoxide. The mechanism of the 4‐ZC6H4O−‐promoted reaction was similar to that of R2NH‐promoted reactions, except that the former proceeded with the 1st step being the rds and the latter proceeded with a change in the rds from the second to the first step with a stronger nucleophile.

Pushing the Upper Limit of Nucleophilicity Scales by Mesoionic N-Heterocyclic Olefins.

A series of mesoionic, 1,2,3-triazole-derived N-heterocyclic olefins (mNHOs), which have an extraordinarily electron-rich exocyclic CC-double bond, was synthesized and spectroscopically characterized, in selected cases by X-ray crystallography. The kinetics of their reactions with arylidene malonates, ArCH=C(CO2 Et)2 , which gave zwitterionic adducts, were investigated photometrically in THF at 20 °C. The resulting second-order rate constants k2 (20 °C) correlate linearly with the reported electrophilicity parameters E of the arylidene malonates (reference electrophiles), thus providing the nucleophile-specific N and sN parameters of the mNHOs according to the correlation lg k2 (20 °C)=sN (N+E). With 21<N<32, the mNHOs are much stronger nucleophiles than conventional NHOs. Some mNHOs even excel the reactivity of mono- and diacceptor-substituted carbanions. It is exemplarily shown that the reactivity parameters thus obtained allow to calculate the rate constants for mNHO reactions with further Michael acceptors and predict the scope of reactions with other electrophilic reaction partners including carbon dioxide, which gives zwitterionic mNHO-carboxylates. The nucleophilicity parameters N correlate linearly with a linear combination of the quantum-chemically calculated methyl cation affinities and buried volumes of mNHOs, which offers a valuable tool to tailor the reactivities of strong carbon nucleophiles.

Mesoionische N‐Heterocyclische Olefine verschieben die obere Grenze der Nucleophilie‐Skala

AbstractMesoionische, 1,2,3‐Triazol‐abgeleitete N‐heterocyclische Olefine (mNHOs) mit außerordentlich elektronenreicher, exocyclischer CC–Doppelbindung wurden synthetisiert und spektroskopisch charakterisiert, z. T. durch Röntgenstrukturanalyse. Die Kinetik der mNHO‐Reaktionen mit Arylidenmalonaten (ArCH=C(CO2Et)2) zu zwitterionischen Addukten wurde photometrisch in THF bei 20 °C verfolgt. Die resultierenden Geschwindigkeitskonstanten 2. Ordnung k2(20 °C) korrelieren linear mit zuvor bestimmten Elektrophilieparametern E der Arylidenmalonate (Referenzelektrophile) und liefern gemäß der Beziehung lg k2(20 °C)=sN(N+E) die nucleophilspezifischen N‐ und sN‐Parameter der mNHOs. Die mNHOs sind mit 21&lt;N&lt;32 viel stärkere Nucleophile als herkömmliche NHOs. Einige mNHOs übertreffen sogar die Reaktivität von mono‐ und diakzeptor‐substituierten Carbanionen. Es wird an Beispielen gezeigt, dass es die so bestimmten Reaktivitätsparameter ermöglichen, die Geschwindigkeitskonstanten für mNHO‐Reaktionen mit weiteren Michael‐Akzeptoren zu berechnen. Auch die Reaktionen mit anderen elektrophilen Reaktionspartnern, inklusive Kohlenstoffdioxid, das zwitterionische mNHO‐Carboxylate bildet, lassen sich vorhersagen. Die Nucleophilie‐Parameter N korrelieren linear mit einer Linearkombination der quantenchemisch berechneten Methylkation‐Affinitäten und %Vbur („buried volumes“) der mNHOs, was ein wertvolles Werkzeug liefert, um Reaktivitäten starker Kohlenstoff‐Nucleophile maßzuschneidern.

Solvation-enhanced electrolyte on layered oxide cathode tailoring even and stable CEI for durable sodium storage

Layered transition-metal oxide materials are ideal cathode candidates for sodium-ion batteries due to high specific energy, yet suffer severe interfacial instability and capacity fading owing to strongly nucleophilic surface. In this work, the interfacial stability of layered NaNi1/3Fe1/3Mn1/3O2 cathode was effectively enhanced by electrolyte optimization. And the interfacial chemistry between the cathode and four widely used electrolytes (EC/DMC, EC/EMC, EC/DEC and EC/PC) was elucidated through experiments and theoretical calculations. The Na+ solvation structures at cathode-electrolyte interface in all four electrolytes exhibited enhanced coordination due to high electron density and strong nucleophilicity of oxide surface, which promoted the electrolytes’ decomposition with decreased oxidation stability. Among them, the EC/DMC electrolyte showed the tightest solvation structure due to smaller molecular chains and stable electrochemistry, which derived an even and robust cathode electrolyte interphase. It effectively protected the cathode and facilitated the reversible Na+ transport during long cycles, enabling the batteries with a high capacity retention of 83.3% after 300 cycles. This work provides new insights into the role of electrode surface characteristics in interface chemistry that can guide the design of advanced electrode and electrolyte materials for rechargeable batteries.

Efficient synthesis of thioquinazolinedione derivatives via the reaction of 2-aminobenzonitrile and carbonyl sulfide catalyzed by NaHS

An efficient method for the synthesis of thioquinazolinediones from 2-aminobenzonitriles and carbonyl sulfide (COS) catalyzed by NaHS was established. In this synthetic method, NaHS was used to catalyze the reaction of COS with a broad range of 2-aminobenzonitrile to form the corresponding thioquinazolinedione. Moreover, the controlled experiments demonstrated that NaHS not only reacted with 2-aminobenzonitrile to form 2-aminobenzothioamide, but also acted as a strong nucleophile to react with COS to form the active intermediate dithiocarbonate. Subsequently, 2-aminobenzothioamide reacted with dithiocarbonate to form the thioquinazolinedione easily. Meanwhile, the generated H2S was recycled as sulfur source and hydrogen source to produce 2-aminobenzothioamide.

Synthesis of tetrazoles through a domino reaction: A molecular electron density theory study of energetics, selectivities, and molecular mechanistic aspects

This study corresponds to a molecular electron density theory (MEDT) investigation to shed light on the energetics, selectivities, and molecular mechanistic aspects of an experimental domino reaction. Theoretical evidences at the M06–2X/6-31G(d) level indicates that this domino reaction includes three different successive steps and is initialized by a stepwise HCl elimination from precursor chlorohydrazone NPCH to yield nitrile imine NI-2. A subsequent stepwise and highly regioselective [3 + 2] cycloaddition (32CA) reaction of NI-2 toward tetramethylguanidine TMG-3 affords corresponding formal [3 + 2] cycloadduct CA-1 as the sole product. Finally, a stepwise HNMe2 elimination experienced by CA-1 leads to amino triazole ATA as an aromatic five-membered target product. Computed rate constants reveal that the HCl elimination step should be considered as the bottleneck of this domino reaction. However, a topological analysis of electron localization function (ELF) of NI-2 demonstrates a zwitterionic type (zw-type) 32 C A reaction is expected between NI-2 and TMG-3. This 32CA reaction also displays an almost noticeable polar character arising from moderate electrophilicity and strong nucleophilicity of NI-2 and TMG-3, respectively. The regioselectivity of 32CA reaction can be explained via analysis of Parr functions values calculated at the reactive sites of reagents. The molecular mechanism of the 32CA reaction was explored through portraying bond forming/breaking patterns involved in this polar, stepwise, and zw-type reaction by means of the ELF analysis. Indeed, formation of both C–N single bonds along the first and second steps takes place through coupling of the corresponding pseudoradical centers.

Chemoselectivity Streamlines the Approach to Linear and Y-Shaped Thiol-Polyethers Starting from Thiocarboxylic Acids.

Thiol-functionalized polyethers, especially poly(ethylene oxide) (PEO), have extensive applications in biomedicine and materials sciences. Herein, we report a simple one-pot synthesis of α-thiol-ω-hydroxyl polyethers through ring-opening polymerization (ROP) of epoxides using thiocarboxylic acid initiators followed by in situ aminolysis. The efficient and chemoselective metal-free Lewis pair catalyst avoids transthioesterification thus achieving well-controlled molar mass, low dispersity, and high end-group fidelity. Kinetic and calculation results demonstrated a fast-initiation mode of the ROP for the strong nucleophilicity of the thiocarboxylate anion and its weak interaction with Lewis acid. The method is expanded for α-thiol-ω-dihydroxyl (Y-shaped) PEO by virtue of the stability of thioester during the ROP. The thiol functionality in linear/Y-shaped PEO is further corroborated by the intensified interaction with gold surface and the resultant protein resistance behavior.

Effective Enzymatic Synthesis of Benzotropolone and Formation Mechanism of Its Bicyclo[3.2.1]octane‐type Intermediate

AbstractIn this study, 1′,2′‐dihydroxy‐3,4‐benzotropolone (BTP), the simplest theaflavins (TFs) derivative, is synthesized via the oxidative coupling of pyrogallol (PG) and catechol (CC). We show that low temperature was beneficial to the production of BTP. A possible generation mechanism of the key bicyclo[3.2.1]octane‐type intermediate (BOI) during the formation process of BTP was subsequently proposed. Our analysis based on quantum chemical calculations indicated that three types of tautomers of PG quinones should be present in the reaction solution. Among them, PG quinone tautomer III (PGQT‐III) with two carbanions might be one of the direct substrates for BOI synthesis, which underwent 1,6‐addition reaction to C3‐C4 bond of ortho‐quinone with strong electrophilicity leading to the key intermediate. Furthermore, the presence of PGQT‐III was also supported by the retrosynthetic analysis of BOI. The findings not only shed light on the production mechanism of BTP, but also create new prospects in synthesizing TFs with controllable products.

Non-Classical Molecular Activation by Phosphines and N-Heterocyclic Carbenes and Its Application to Catalytic Reactions

Abstract This Award Account reports our recent studies concerning the catalytic transformations that involve a non-classical mode of molecular activation by tertiary phosphines and N-heterocyclic carbenes (NHCs). Regarding organophosphine catalysis, we successfully designed reactions based on a P(III)/P(V) redox couple. A catalytic protocol for generating pentacoordinate P(V) species was devised by the reaction of tertiary phosphines, acyl fluorides and alkynoates. The ability of the thus generated fluorophosphoranes to participate in ligand coupling and ligand metathesis with organosilicon nucleophiles enables synthetic transformations that are otherwise unattainable, including the intermolecular carbofluorination of alkynes and the hydroalkenylation of enol ethers. Regarding nucleophilic NHC catalysis, the use of imidazolium-based NHCs can generate deoxy-Breslow intermediates that are sufficiently nucleophilic to promote the aromatic substitution of aryl halides, aryl ethers and anilides. The protocol can also be used for the nucleophilic activation of styrene derivatives, allowing for the generation of a series of ylide intermediates that can serve as non-stabilized vinyl anion equivalents. These results demonstrate that synthetic transformations involving non-stabilized carbanions can be conducted under catalytic conditions without the use of strong organometallic nucleophiles.

Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis.

Organic molecules that can be connected to multiple substrates by sequential C-C bond formations can be utilized as linchpins in multicomponent processes. While they are useful for rapidly increasing molecular complexity, most of the reported linchpin coupling methods rely on the use of organometallic species as strong carbon nucleophiles to form C-C bonds, which narrows the functional group compatibility. Here, we describe a metal-free, radical-mediated coupling approach using a formyl-stabilized phosphonium ylide as a multifunctional linchpin under visible-light photoredox conditions. The present method uses the ambiphilic character of the phosphonium ylide, which serves as both a nucleophilic and an electrophilic carbon-centered radical source. The stepwise and controllable generation of these radical intermediates allows sequential photocatalysis involving two mechanistically distinct radical additions, both of which are initiated by the same photocatalyst in one pot with high functional group tolerance. The methodology enables a bidirectional assembly of the linchpin with two electronically differentiated alkene fragments and thus offers rapid and modular access to 1,4-dicarbonyl compounds as versatile synthetic intermediates.

Substitution of H Atoms in Unsaturated (Vinyl-Type) Carbocations by Cl or O Atoms.

Introduction of Cl and O atoms into C4-vinyl carbocations was studied by X-ray diffraction analysis and IR spectroscopy. Chlorine atoms are weak electron acceptors in ordinary molecules but, within vinyl carbocations, manifest themselves as strong electron donors that accept a positive charge. The attachment of a Cl atom directly to a C=C bond leads to an increase in the e-density on it, exceeding that of the common double bond. The positive charge should be concentrated on the Cl atom, and weak δ- may appear on the C=C bond. More distant attachment of the Cl atom, e.g., to a C atom adjacent to the C=C bond, has a weaker effect on it. If two Cl atoms are attached to the Cγ atom of the vinyl cation, as in Cl2CγCδHCαHCH3, then the cation switches to the allyl type with two practically equivalent and almost uncharged CγCδCα bonds. When such a strong nucleophile as the O atom is introduced into the carbocation, a protonated ester molecule with a C-O(H+)-C group and a C=C bond forms. Nonetheless, in the future, there is still a possibility of obtaining carbocations with a non-protonated C-O-C group.